Ethanol gas sensor based on Al-doped ZnO nanomaterial with many gas diffusing channels

ZnO nanomaterial with multi-microstructures is synthesized by using normal pressure thermal evaporation and then doped with different Al₂O₃ contents by grinding in an agate mortar. The as-prepared Al-doped ZnO nanomaterials are characterized by X-ray diffraction and scanning electron microscopy. The characterization results show that all the compounds are wurtzite with hexagonal structure and are well crystallized. Channels/connecting holes arising from many kinds of ZnO microstructures are abundant. Both annealing and Al₂O₃-doping contributes to an increase in the quasi-one-dimensional and tri-dimensional microstructures. The as-prepared Al-doped ZnO nanomaterials show excellent gas responses to ethanol. The sensing mechanism of the ZnO-based nanomaterials with multi-microstructures is further analyzed by using the Effective Specific Surface Model. Excellent sensitivity (200) companied with short response time (8 s) and recovery time (10 s) to 3000 ppm ethanol is obtained with a ZnO-based sensor with 2 at.% Al₂O₃ at the operating temperature of 290 °C after the sensor is annealed at 500 °C.     

A single ZnO tetrapod-based sensor

Transferable ZnO tetrapods were grown by an aqueous solution method. An individual ZnO tetrapod-based sensor was fabricated by in situ lift-out technique and its ultraviolet (UV) and gas sensing properties were investigated. This single tetrapod-based device responds to the UV light rapidly and showed a recovery time of about 23 s. The sensitivity of a single ZnO tetrapod sensor to oxygen concentration was also investigated. We found that when UV illumination is switched off, the oxygen chemisorption process will dominate and assists photoconductivity relaxation. Thus relaxation dynamics is strongly affected by the ambient O₂ partial pressure as described.We also studied the response of ZnO tetrapod-based sensor in various gas environments, such as 100 ppm H₂, CO, i-butane, CH₄, CO₂, and SO₂ at room temperature. It is noted that ZnO tetrapod sensor is much more sensitive to H₂, i-butane and CO. It is demonstrated that a ZnO tetrapod exposed to both UV light and hydrogen can provide a unique integrated multiterminal architecture for novel electronic device configurations.     

Pinecone-shaped ZnO nanostructures: Growth, optical and gas sensor properties.

Pinecone-shaped ZnO nanostructures have been fabricated on Si substrate by pulsed laser deposition. The scanning electron microscope images showed that pinecone-shaped ZnO nanostructure was 6-fold symmetry and has the rough surface on one end. X-ray diffraction, Raman spectra and X-ray photoelectron spectroscopy indicated that the ZnO nanostructures have high crystal quality and a large amount of surface states. Compared with ZnO nanowires and nanobelts, the oxygen gas sensor based on pinecone-shaped ZnO nanostructures has excellent selectivity, fast response and recover, and lower operating temperature. Meanwhile, the response properties are very stable over several circles.     

Humidity sensor based on LiCl-doped ZnO electrospun nanofibers

The humidity sensitive characteristics of sensors fabricated from pure ZnO nanofibers and LiCl-doped ZnO composite fibers by screen-printing on ceramic substrates with carbon interdigital electrodes have been investigated. The best result is obtained for 1.2 wt% LiCl-doped sample, which exhibits high humidity sensitivity, rapid response and recovery, small hysteresis, excellent linearity, and good reproducibility. The impedance of the sensor varies more than four orders of magnitude during the whole relative humidity (RH) from 11 to 95%. The response time and recovery time of the sensor is about 3 and 6 s, respectively. These results make our product a good candidate in fabricating high performance humidity sensors.     

基于微接触印刷的ZnO紫外传感器特性研究

采用微接触印刷技术和水热生长方法在硅基底上实现了ZnO种子层的图案化转移与纳米线阵列的可控制备。利用X射线衍射(XRD)、能量色散谱(EDS)和扫描电子显微镜(SEM)等测试手段对制备的ZnO纳米线晶体结构、化学组分以及表面形貌进行了表征,并对制备的ZnO纳米线传感器进行了紫外特性测试。测试结果表明:随着紫外光强度的增加,传感器的光暗电流比和光响应度也随之增加。当紫外传感器偏压在4.5 V时,其光暗电流比为80.8,响应度可达4.05 A/W。     

基于环形微热板的ZnO微气体传感器设计

提出一种新型的设有环形结构微热板的硅基ZnO微气体传感器。利用ANSYS软件,将环形电极结构与传统的蛇形结构进行温度分布的模拟仿真,发现该结构能供给传感器更高的温度且中心温度分布均匀,进而解决了现有传感器功耗大的缺点。通过对RF磁控溅射ZnO薄膜的工艺摸索,得出了适宜作气敏薄膜的制备参数。该传感器在250℃下对（200-1000）×10-6CH4气体有很好的响应。     

Improved selective acetone sensing properties of Co-doped ZnO nanofibers by electrospinning

Pure and Co-doped (0.3 wt%, 0.5 wt%, and 1 wt%) ZnO nanofibers are synthesized by an electrospinning method and followed by calcination. The as-synthesized nanofibers are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) spectroscopy. Comparing with pure ZnO nanofibers, Co-doped nanofibers exhibit improved acetone sensing properties at 360 °C. The response of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone is about 16, which is 3.5 times larger than that of pure nanofibers (about 4.4). The response and recovery times of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone are about 6 and 4 s, respectively. Moreover, Co-doped ZnO nanofibers can successfully distinguish acetone and ethanol/methanol, even in a complicated ambience. The high response and quick response/recovery are based on the one-dimensional nanostructure of ZnO nanofibers combining with the Co-doping effect. The selectivity is explained by the different optimized operating temperatures of Co-doped ZnO nanofibers to different gases.     

氧化锌纳米棒/单晶硅的酒精传感器研究

首先采用射频溅射在单晶硅(Si)上制备氧化锌(ZnO)薄膜,作为生长ZnO纳米棒的晶种层,再在水热条件下生长ZnO纳米棒.X射线衍射、X射线能量色散谱,扫描电镜及室温光致发光谱对样品的物相结构、成分、表面微观形貌和晶体缺陷进行了表征.结果表明合成的ZnO纳米棒是六方纤锌矿结构,长径比较高,结晶良好.研究了ZnO纳米棒/单晶Si传感器在空气和酒精气体中的电压-电流(Ⅰ-Ⅴ)特性,阻抗谱及响应-恢复时间.该传感器在+6 V的偏置电压下,其电阻在0.08 g/L酒精气体中下降71%,响应时间小于1 min,可以作为一种新型的酒精气体传感器.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.     

High sensitive and selective formaldehyde sensors based on nanoparticle-assembled ZnO micro-octahedrons synthesized by homogeneous precipitation method

Nanoparticle-assembled ZnO micro-octahedrons were synthesized by a facile homogeneous precipitation method. The ZnO micro-octahedrons are hexagonal wurtzite with high crystallinity. Abundant structure defects were confirmed on ZnO surface by photoluminescence. Gas sensors based on the ZnO micro-octahedrons exhibited high response, selectivity and stability to 1–1000 ppm formaldehyde at 400 °C. Especially, even 1 ppm formaldehyde could be detected with high response (S = 22.7). It is of interest to point out that formaldehyde could be easily distinguished from ethanol or acetaldehyde with a selectivity of about 3. The high formaldehyde response is mainly attributed to the synergistic effect of high contents of electron donor defects (Zn_i and V_O) and highly active oxygen species (O²⁻) on the ZnO surface.     

Pure and Pt-loaded gamma iron oxide as sensor for detection of sub ppm level of acetone

In this study, pure and Pt-loaded nanocrystalline γ-Fe₂O₃ have been prepared by precipitation using ultrasonic irradiation. The synthesized powders were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), transmission electron micrograph (TEM), selected area electron diffraction (SAED), scanning electron microscope (SEM) and energy dispersive X-ray (EDX). Pure nanocrystallline γ-Fe₂O₃ sensors were found to show good response towards sub ppm level of acetone at 250 °C, and improves significantly on Pt loading. As an example, 1 wt% Pt loading of nanocrystallline γ-Fe₂O₃ increased its response towards acetone by 55%. The high response of γ-Fe₂O₃ holds it as a potentially promising candidate for acetone detection which may lead for the non-invasive testing of diabetics.     

Acetylene sensor based on Pt/ZnO thick films as prepared by flame spray pyrolysis

ZnO nanoparticles loaded with 0.2-2.0 at.% Pt have been successfully produced in a single step by flame spray pyrolysis (FSP) technique using zinc naphthenate and platinum(II) acetylacetonate, as precursors dissolved in xylene and their acetylene sensing characteristics have been investigated. The particle properties were analyzed by XRD, BET, TEM, SEM and EDS. Under the 5/5 (precursor/oxygen) flame condition, ZnO nanoparticles and nanorods were observed. The crystallite sizes of ZnO spherical and hexagonal particles were found to be ranging from 5 to 20 nm while ZnO nanorods were seen to be 5-20 nm in width and 20-40 nm in length. In addition, very fine Pt nanoparticles with diameter of ∼1 nm were uniformly deposited on the surface of ZnO particles. From gas-sensing characterization, acetylene sensing characteristics of ZnO nanoparticles is significantly improved as Pt content increased from 0 to 2  at.%. The 2 at.% Pt loaded ZnO sensing film showed an optimum C₂H₂ response of ∼836 at 1% acetylene concentration and 300 °C operating temperature. A low detection limit of 50 ppm was obtained at 300 °C operating temperature. In addition, Pt loaded ZnO sensing films exhibited good selectivity towards hydrogen, methane and carbon monoxide.     

Selective detection of HCHO gas using mixed oxides of ZnO/ZnSnO3

Mixed oxides of ZnO/ZnSnO₃ doped with Au element were prepared by a hydrothermal process. The crystal structure, composition and ceramic microstructure of the powders obtained were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show that the product is the mixture of ZnO/ZnSnO₃; its particle size is about 500 nm with good dispersivity in shape. The sensitivity, selectivity, response and recovery properties of the ZnO/ZnSnO₃-based sensors were investigated by mixing a target gas in air. It is found that the sensors have remarkable sensitivity to HCHO vapor and satisfactory selectivity to other gases.     

类积木状ZnO气体传感器的制备及其气敏特性研究

采用水热法合成了类积木状ZnO纳米结构,利用X射线衍射仪(XRD)、X射线能谱分析仪(EDS)和扫描电子显微镜(SEM)对制备的ZnO纳米结构的物相、化学组分及微观形貌进行了表征与分析。对基于ZnO纳米结构的气体传感器进行甲烷气敏特性测试,测试结果表明:该传感器的最佳工作电压为5 V,在该电压下对体积分数为200×10-6甲烷气体的灵敏度可高达55.4%,最低检测限为1×10-6。     

Fabrication of gas sensing devices with ZnO nanostructure by the low-temperature oxidation of zinc particles

A method for low-temperature synthesis of a mixture of high-density ZnO nanoflakes and nanowires was developed to produce low-cost and high-efficiency gas sensors with ZnO nanostructures. ZnO nanoflakes and nanowires were grown on glass substrates by the RF sputter deposition of Zn particles and localized oxidation at a low temperature of 300 °C. The synthesized ZnO nanoflakes and nanowires were polycrystalline and had nanometer dimensions, as revealed by X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM) measuring. A gas sensor based on the mixture of ZnO nanoflakes/nanowires responded rapidly and sensitively to ethanol. The sensing properties of the ZnO nanostructure sensor were approximately 72% for 50 ppm ethanol gas at an operating temperature of 100 °C. The response to 10 ppm of ethanol gas was 42% at the same temperature.     

氧等离子体处理ZnO纳米纤维材料的制备及其对丙酮气敏性能的研究

采用静电纺丝法制备了ZnO纳米纤维材料并使用氧等离子体对其进行表面处理.通过X射线衍射(XRD),扫描电子显微镜(SEM),BET比表面积测试以及X射线光电子能谱分析(XPS)等手段对样品的结构与形貌进行了表征分析.将氧等离子体处理前后的ZnO纳米纤维分别制成气体传感器,对浓度为1×10-6~100×10-6(体积分数)丙酮气体的敏感特性进行了测试分析.测试结果表明,氧等离子体处理后的ZnO纳米纤维响应值较未处理的ZnO纳米纤维有大幅度的提升,最佳工作温度也有所降低,且对甲醛、苯、甲苯、二甲苯等几种干扰气体表现出更好的选择性.从晶粒间势垒和耗尽层厚度等角度初步分析了氧等离子体处理改善ZnO气敏特性的机理.     

Nano particulate SnO2 based resistive films as a hydrogen and acetone vapour sensor

SnCl₂ (solution) was spin coated on soda lime glass and Al₂O₃ substrate to obtain nano-particulate tin oxide film, directly by sintering at 550 °C for 40 minutes (min). The surface morphology and crystal structure of the tin oxide films were analyzed using atomic force microscopy (AFM) and X-ray diffraction (XRD). The size of SnO₂ nanostructure was determined from UV-vis and found to be ?3 nm. These films were tested for sensing H₂ concentration of 0.1-1000 ppm at optimized operating temperature of 265 °C. The results showed that sensitivity (R_air/R_gas per ppm) goes on increasing with decreasing concentration of test gas, giving concentration dependent changes. Special studies carried out at low concentration levels (0.1-1 and 1-10 ppm) of H₂, give high sensitivity (200 × 10⁻³/ppm) for lowest concentration (0.1-1 ppm) of H₂. The selectivity for H₂ against relative humidity (RH), CO₂, CO and LPG gases is also good. The sensor, at operating temperature of 200 °C, is showing nearly zero response to 300 ppm of H₂, and offering response to acetone vapour of 11 ppm. Selectivity for acetone against RH% and CO₂ was also studied. These sensors can be used as H₂ sensor at an operating temperature of 265 °C, and as an acetone sensor at the operating temperature of 200 °C.     

Using a TiO2/ZnO double-layer film for improving the sensing performance of ZnO based NO gas sensor

NO gas sensors, based on ZnO thin film (ZnO_film), TiO₂ nanoparticulate film (TiO₂NP), and TiO₂NP/ZnO_film double-layer film, were fabricated, and their sensing characteristics towards NO gas were investigated in this study. The maximal response of a ZnO_film deposited onto a rougher Al₂O₃ substrate, towards NO gas, was higher than that of a ZnO_film deposited on a smoother glass substrate. Although the sensing response of the TiO₂NPs itself towards NO gas was minute, the TiO₂NP/ZnO_film double-layer film showed enhanced response as compared with TiO₂NP or ZnO_film single-layer film. In addition, the sensor response of the TiO₂NP/ZnO_film double-layer film was strongly influenced by the annealing time for the film preparation; the maximum response to NO was enhanced about 6.2 times as the annealing time was increased from 30 min to 2 h. Based on the XPS results, the increase in the transition zone between TiO₂NP and ZnO_film along with the appearance of Ti³⁺ state was noticed when the annealing time was increased. With the high sensitive TiO₂NP/ZnO_film/Al₂O₃ electrode, the limit of detection (S/N = 3) can be achieved at 8.8 ppb. The double-layer TiO₂NP/ZnO_film also showed improved selectivities with respect to NO₂ and CO.     

WO3 nanocrystals: Synthesis and application in highly sensitive detection of acetone

WO₃ nanocrystals have been prepared by a sol-gel route and characterized by X-ray diffractometry, scanning electron microscopy, and transmission electron microscopy. The experimental results show that WO₃ nanocrystals have a high crystallographic quality and a good dispersivity. The particles’ sizes are in the range of 25-100 nm. The fabricated WO₃ nanocrystal-based sensors have an excellent sensitivity and selectivity to acetone, and display a rapid response and recovery characteristics. The developed sensors exhibit a detection limit down to 0.05 ppm at 300 °C, rendering a promising application in noninvasive diagnosis of diabetes. The response mechanism of the WO₃ nanocrystal sensor to low concentration of acetone has been discussed based on the depletion layer model.     

CdO activated Sn-doped ZnO for highly sensitive, selective and stable formaldehyde sensor

Sn-, Ni-, Fe- and Al-doped ZnO and pure ZnO are prepared by coprecipitation method, and characterized by scanning electron microscope (SEM), energy diffraction spectra (EDS) and X-ray diffraction (XRD). Their formaldehyde gas sensing properties are evaluated and the results show that 2.2 mol% Sn dopant can increase the response of ZnO by more than 2 folds, while other dopants increase little response or even decrease response. Further, CdO is used to activate ZnO based formaldehyde sensing material. It is demonstrated that 10 mol% CdO activated 2.2 mol% Sn-doped ZnO has the highest formaldehyde gas response, with a linear sensitivity of ∼10/ppm at lowered work temperature of 200 °C than 400 °C of pure ZnO, and high selectivity over toluene, CO and NH₃, as well as good stability tested in 1 month.